CN108395536A - A kind of preparation method of epithio monomer and the unidextrality polythiaether with skeleton structure - Google Patents
A kind of preparation method of epithio monomer and the unidextrality polythiaether with skeleton structure Download PDFInfo
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Abstract
The present invention relates to a kind of epithio monomer and the preparation method of the unidextrality polythiaether with skeleton structure, belong to unidextrality spiral macromolecule preparation field.Unidextrality polythiaether forms unidextrality spiral polythiaether after the optically-active episulfide compounds anionic ring-opening polymerization with 3 diaryl-amine base, 1,2 epithio propane skeleton structure.This kind of optically-active episulfide compounds, first with optically-active epichlorohydrin reaction, are then made with the effect of thiocyanation amine by diaryl-amine.The molecular weight distribution (Mw/Mn) of the unidextrality spiral polythiaether with poly- [3 diaryl-amine base, 1,2 epithio propane] skeleton structure is 1.13 1.22 or so made from this method.Polymer exists with unidextrality helical structure in the solution, on the contrary, the absolute value of specific rotation is 35 times of monomer, CD signal strengths are 15 times of monomer or more for the optical direction of polymer and the direction of monomer.
Description
Technical field
The present invention relates to a kind of epithio monomer and the preparation method of the unidextrality polythiaether with skeleton structure, belong to singlehanded
Property spiral macromolecule preparation field.
Background technology
Unidextrality spiral macromolecule with optical activation shows some unique performances, as molecular chiral identifies energy
Power, asymmetry catalysis ability etc., and show potential application prospect etc. in biomedical sector.Therefore, optically active list
Chiral helical type polymer becomes the research object that people extremely pay close attention to.
Optically active unidextrality spiral macromolecule is segmented into two classes by its source to be divided to, and one kind is natural optical activity spiral shell
Revolve macromolecule, another kind of artificial synthesized spiral high-molecular compound.Natural unidextrality spiropolymer since its type is limited,
And difficulty is isolated and purified, cost is higher, it is difficult to mass produce, and the diversity of structure is also far from the asymmetry for meeting people
The demand of catalysis and chiral Recognition, and then there is artificial synthesized unidextrality spiropolymer structure can design, it is wide in variety, easily expand
The features such as big production, therefore, artificial synthesized unidextrality spiropolymer are one of the research hotspots in the field now.
Okamoto uses the method for spiral selective polymerisation to polymerize to have obtained molten by metering system triphenyl phosphate methyl esters first
The polymethyl triphenyl phosphate methyl esters (J.Am.Chem.Soc.1979,101,4763) that unidextrality helical structure is kept in liquid, with
The polymethyl triphenyl phosphate methyl esters of this unidextrality spiral be may be used as into high performance liquid chromatography (HPLC) chiral stationary phase afterwards,
To separation of racemate (J.Am.Chem.Soc.1980,102,6358；J.Am.Chem.Soc., 1981,103,6971).It is existing
In chiral stationary phase successful commercialization.In addition, Reggelin et al. reports the spiral PTrMA based on Okamoto for the first time
The asymmetric catalysis (Proc.Natl.Acad.Sci., U.S.A., 2004,101,5461-5466) of class.Relative to small point
Sub- chiral catalyst, the advantage that Polymer supported chiral catalysts have recycling easy, economic.
Up to the present, the polymer for keeping stable unidextrality helical structure in the solution of report has：Polyacrylamide
Class (J.Polym.Sci.：Part A：Polymer Chemistry, 2010,48,5411-5418), polycarbodiimide class
(Macromolecules 2010,43,1867-1873), polyacetals class (J.Polym.Sci., Part A：
Polym.Chem.2000,38,2623), Polyisocyanate esters (Polym.J.1993,25,391), polyacetylene class
(Macromolecules, 2,007 40, No.19；Macromolecules 2000,33,3978), poly- isonitrile class
(Angew.Chem., Int.Ed.Engl.1996,35,1554), poly- aryne class (Angew.Chem., Int.Ed.Engl.1996,
35,2111) etc..Wherein, the poly- isonitrile of unidextrality spiral obtained United States Patent (USP) (US 7619109B2) in 2009.In addition,
Especially it should be mentioned that：Patent about spiral polyethers was authorized (CN by this seminar in 2012
201010101435.7)。
The patent mainly introduces a kind of polyethers with fluorenyl, and structural formula is shown below：
In formula, R is alkyl, aryl or other alkyl；The other positions of fluorenes ring can also be with substituent group；R1Be alkyl or
Hydrogen atom；M is integer.
2014, this seminar obtained other one license (CN 201410053065.2) about spiral polyethers.
The patent mainly introduces a kind of polyethers with diaryl-amine base, and structural formula is shown below：
In formula：Ar is phenyl ring or aryl；The degree of polymerization of n=8~10.Can be carried when Ar is phenyl ring, on phenyl ring hydrogen atom or
Substituent group.
Invention content
The object of the present invention is to provide a kind of unidextralities with poly- [3- diaryl-amine base -1,2- epithios propane] skeleton structure
Spiral polythiaether and preparation method thereof.
A kind of preparation method of epithio monomer, which is characterized in that the structural formula of the epithio monomer is Formula II or formula
III,
Wherein R1, R2, R3, R4, R5, R6, R7, R8, R9, R10 be hydrogen atom either alkyl or R1, R2, R3, R4,
It is one or more phenyl ring at adjacent two in R5, R6, R7, R8, R9, R10；
Preparation method includes：
It is reacted in the presence of acetic acid with the epoxychloropropane of optically-active using diaryl-amine and generates open-loop products, then in sodium hydroxide
In the presence of carry out closed loop, obtain the epoxy monomer of optically-active；
The epoxy monomer of optically-active is dissolved into organic solvent, thiocyanation amine aqueous solution is added and carries out that optically-active is obtained by the reaction
Epithio monomer, a concentration of 40-60mmol/10mLH of the thiocyanation amine aqueous solution2O。
Preferably, the preparation method of epithio monomer of the invention, the organic solvent is cyclic ethers class or has loop configuration
Hydro carbons.
Preferably, the preparation method of epithio monomer of the invention, the hydro carbons are hexamethylene or toluene.
The preparation method of the present invention also provides a kind of unidextrality spiral polythiaether with skeleton structure has skeleton structure
Unidextrality spiral polythiaether have Formulas I shown in poly- [3- diaryl-amine base -1,2- epithios propane] skeleton structure, polymer is R
Type or S types,
In formula：Y1, Y2, Y3, Y4 are phenyl ring or aryl or the phenyl ring containing substituent group or aryl；N be the degree of polymerization=8~
10；
The preparation method includes：
Epithio monomer is obtained using the preparation method of above-mentioned epithio monomer；
Epithio monomer is heated to polymerization under initiator initiation, obtains that there is poly- [3- diaryl-amine bases -1,2- epoxy third
Alkane] skeleton structure unidextrality spiral polythiaether.
Preferably, the preparation method of the unidextrality spiral polythiaether with skeleton structure of the invention, the initiator are
Alkali metal hydroxide, metal-alcoholates compound or metallic alkide compound.
Preferably, the preparation method of the unidextrality spiral polythiaether with skeleton structure of the invention, it is characterised in that：Add
Temperature when thermal polymerization is 70-250 DEG C.
With the unidextrality helix poly with poly- [3- diaryl-amine base -1,2- epithios propane] skeleton structure prepared by this method
Thioether exists with unidextrality helical structure in the solution, and the optical direction of polymer is with monomer on the contrary, the absolute value of specific rotation is
3-5 times of monomer, CD signal strengths are 15 times of monomer or more.
Description of the drawings
Fig. 1 is the CD spectrograms of Example 1 and Example 2 of the present invention monomer and polymer；
Fig. 2 is the CD spectrograms of the embodiment of the present invention 3 and 4 monomer of embodiment and polymer；.
Specific implementation mode
There is one kind the unidextrality spiral polyethers of poly- [3- diaryl-amine bases -1,2- propylene oxide] skeleton structure to have Formulas I institute
The skeleton structure shown
In formula：Ar is phenyl ring or aryl；The degree of polymerization of n=8~10.Can be carried when Ar is phenyl ring, on phenyl ring hydrogen atom or
Substituent group；Polymer is R types or S types, has unidextrality helical structure.
One kind having the preparation side of the unidextrality spiral polythiaether of poly- [3- diaryl-amine base -1,2- epithios propane] skeleton structure
Method：
1) it, is reacted in the presence of acetic acid with the epoxychloropropane of optically-active with diaryl-amine and generates open-loop products, then in hydroxide
Closed loop in the presence of sodium obtains the epoxy monomer of optically-active, then is reacted with thiocyanation amine, obtains the epithio monomer of optically-active；
R in formula1、R2、R3、R4、R5、R6、R7、R8、R9、R10It can be hydrogen atom, can also be substituent group, it can be at phenyl ring
For multiple phenyl ring arranged side by side.
2), cause the optically-active episulfide compounds II with 3- diaryl-amine base -1,2- propylene oxide skeleton structures with initiator
Or III heats polymerization in ontology or solution, obtains the one hand with poly- [3- diaryl-amine base -1,2- epithios propane] skeleton structure
Property spiral polythiaether I.
It is used in the polymerization process of the optically-active episulfide compounds with 3- diaryl-amine base -1,2- epithio propane skeleton structures
Initiator be alkali metal hydroxide, metal-alcoholates compound or metallic alkide compound.
The solvent used in polymerisation in solution is cyclic ethers class, and such as tetrahydrofuran can also be hydro carbons, such as hexamethylene or first
Benzene.
Bulk polymerization temperature is 150-250 DEG C.
Solution polymerization temperatures are 70-200 DEG C.
Obtain the spiral polyethers that diaryl-amine base is contained in end, core be introduced on the nitrogen-atoms of secondary amine it is photoactive
Epithio group.The present invention has designed and synthesized the chiral episulfide compounds with structure shown in II and III thus：
The position of phenyl ring can be other aryl in II and formula III；R1、R2、R3、R4、R5、R6、R7、R8、R9、R10Can be
Hydrogen atom can also be other alkyl.II is R configurations, and III is S configurations.
The characteristics of structure shown in II and III is that a chiral epithio group is introduced on nitrogen-atoms, and skeleton is as shown in IV：
The position of phenyl ring can be other aryl in formula.
After introducing such a skeleton, the skeleton of II and III are respectively V and VI.
The position of phenyl ring can be other aryl in formula.
Episulfide compounds with skeleton structure shown in V or VI can obtain the unidextrality of the base containing diaryl-amine after polymerization
Spiral polythiaether.
The synthetic method of the episulfide compounds of this optically-active is by the compound elder generation with structure shown in VII and chiral epoxy
Chloropropane reacts, and the episulfide compounds of optically-active is then obtained by the reaction with thiocyanation amine, reaction equation is as shown in reaction equation one：
The position of phenyl ring can be other aryl in formula；R1、R2、R3、R4、R5、R6、R7、R8、R9、R10Can be hydrogen atom,
Can also be other alkyl.
The configuration of gained episulfide compounds determines by the configuration of chiral epichlorohydrin, polarimetry purity and epoxychloropropane
Unanimously.
Optically-active epoxide II and III anion with 3- diaryl-amine base -1,2- epithio propane skeleton structures draws
It sends out agent and causes polymerization, obtain the unidextrality spiral polythiaether with poly- [3- diaryl-amine base -1,2- epithios propane] skeleton structure
VIII.Polymerisation is as shown in reaction equation two：
VIII is in unidextrality spiral (left hand helix or right-handed helix) structure in the solution.The direction of helical structure is by list
The configuration of body episulfide compounds determines.It is positive spiral polythiaether that optically-active symbol is obtained after II polymerizations, and optically-active is obtained after III polymerizations
Symbol is the spiral polythiaether born.
Anionic initiator employed in polymerisation is alkali metal hydroxide, metal-alcoholates compound or metallic alkide
Object.
It can also be polymerisation in solution that polymerization, which can be bulk polymerization, and polymerization temperature is at 70-250 DEG C, preferably 100-150
℃。
The following further explanation to the present invention in conjunction with specific embodiments.
Embodiment 1：
The present embodiment provides the synthesis of (R) -3- (4,4 '-dimethyl) hexichol amido -1,2- epithio propane polymer；
In 100mL round-bottomed flasks, diphenylamines (10.0g, 59mmol), (R)-epoxychloropropane (12.01g is added
130mmol, e.e.：99.0%), 98% acetic acid of 3mL stirs 48 hours in 60-63 DEG C.Then water (40mL) is added, then uses second
Ether (90mL) extracts, and after diethyl ether solution is dried with anhydrous sodium sulfate, powdered sodium hydroxide (6.0g) is added in filtering, and reflux 2 is small
When after filter, be removed under reduced pressure ether, residue obtains yellow with pillar layer separation (eluant, eluent: petrol ether/ethyl acetate 10: 1)
Grease (R) -3- (4,4 '-dimethyl) hexichol amido -1,2- propylene oxide.Above-mentioned propylene oxide (10mmol) is taken to be dissolved in
100mL THF stir 36h at room temperature, are then added water (10mL), then with ether (20mL × 3) extraction, and diethyl ether solution is with anhydrous
After sodium sulphate drying, filtering is removed under reduced pressure ether, residue with pillar layer separation (eluant, eluent: petrol ether/ethyl acetate 10:
1) yellow oil, yield 43.5%, are obtained.(c=1mg/mL, THF), e.e.：98.2%)；1H NMR
(400MHz, CDCl3) δ 7.08 (d, J=8.0Hz, 4H), 6.91 (d, J=8.1Hz, 4H), 4.16 (m, 1H), 3.53 (m, 1H),
3.28-3.08 (m, 1H), 2.42 (m, 1H), 2.30 (m, 6H), 2.05 (m, 1H)13C NMR (100MHz, CDCl3) δ 145.56,
131.17 130.04,121.09,57.98,31.84,25.45,20.71.
Pure epithio monomer and proper proportion levigate KOH powder in an inert atmosphere are added in reaction tube, sets
It in small autoclave, is vacuumized after argon gas displacement, heating stirring takes out test tube after 24 hours in 150 DEG C of constant temperature baths, and addition contains
The THF for having appropriate a small amount of diluted acid, makes reactant dissolve, is then added drop-wise to the solution in the methanol for the 8 times of volumes that stirred,
Gained precipitation filtering, methanol washs repeatedly, and polymerization can be re-dissolved in THF to lay equal stress on and be deposited in methanol and be purified, polymerization product
It is dried in vacuo at 60 DEG C, weighs, be subsequently used for every test, resulting polymers parameter is shown in Table one.
Embodiment 2：
The present embodiment provides the synthesis of (S) -3- (4,4 '-dimethyl) hexichol amido -1,2- epithio propane polymer；
In 100mL round-bottomed flasks, diphenylamines (10.0g, 59mmol), (S)-epoxychloropropane (12.01g is added
130mmol, e.e.：99.0%), 98% acetic acid of 3mL stirs 48 hours in 60-63 DEG C.Then water (40mL) is added, then uses second
Ether (90mL) extracts, and after diethyl ether solution is dried with anhydrous sodium sulfate, powdered sodium hydroxide (6.0g) is added in filtering, and reflux 2 is small
When after filter, be removed under reduced pressure ether, residue obtains yellow with pillar layer separation (eluant, eluent: petrol ether/ethyl acetate 10: 1)
Grease (S) -3- (4,4 '-dimethyl) hexichol amido -1,2- propylene oxide.Above-mentioned propylene oxide (10mmol) is taken to be dissolved in
In 100mL hexamethylenes, thiocyanation amine aqueous solution (50mmol/10mL H are added2O), 36h is stirred at room temperature, and water is then added
(10mL), then extracted with ether (20mL × 3), after diethyl ether solution is dried with anhydrous sodium sulfate, ether is removed under reduced pressure in filtering, residual
Excess obtains yellow oil with pillar layer separation (eluant, eluent: petrol ether/ethyl acetate 10: 1), and yield is 42.6%. [a]
20365=-85 ° of (c=1mg/mL, THF, e.e.：98.1%).
Pure epithio monomer and proper proportion levigate KOH powder in an inert atmosphere are added in reaction tube, sets
In small autoclave, vacuumizing after argon gas displacement, polymerize in 200 DEG C of constant temperature baths, heating stirring takes out test tube after 24 hours,
The THF containing appropriate a small amount of diluted acid is added, so that reactant is dissolved, then which is added drop-wise to the first for the 9 times of volumes that stirred
In alcohol, gained precipitation filtering, methanol washs repeatedly, and polymerization can be re-dissolved in THF to lay equal stress on and be deposited in methanol and be purified, and gather
It closes product to be dried in vacuo at 60 DEG C, weighs, be subsequently used for every test, resulting polymers parameter is shown in Table one.
Embodiment 3：
The present embodiment provides the synthesis of (R) -3- (N- phenyl-N- benzyls) -1,2- epithio propane polymer；Justify in 100mL
In the flask of bottom, Phenhenzamine (11.0g, 60mmol), (R)-epoxychloropropane (12.01g 130mmol, e.e. is added：
99.0%), 98% acetic acid of 3mL stirs 48 hours in 60-63 DEG C.Then water (40mL) is added, then is extracted with ether (90mL),
After diethyl ether solution is dried with anhydrous sodium sulfate, powdered sodium hydroxide (6.0g) is added in filtering, and reflux is filtered after 2 hours, is depressurized
Ether is removed, residue obtains yellow oil (R) -3- with pillar layer separation (eluant, eluent: petrol ether/ethyl acetate 10: 1)
(4,4 '-dimethyl) hexichol amido -1,2- propylene oxide.It takes above-mentioned propylene oxide (10mmol) to be dissolved in 100mL THF, is added
Thiocyanation amine aqueous solution (40mmol/10mL H2O), 36h is stirred at room temperature, water (10mL) is then added, then with ether (20mL
× 3) it extracts, after diethyl ether solution is dried with anhydrous sodium sulfate, ether, residue pillar layer separation (elution is removed under reduced pressure in filtering
Agent: petrol ether/ethyl acetate 10: 1), (R) -3- (N- phenyl-N- benzyl) -1,2- propylene oxide is obtained：Yellow oil, production
Rate 40.8%,(c=1mg/mL, THF, e.e.：98.3%),1H NMR (400MHz, CDCl3)δ7.28
(dq, J=14.2,7.1Hz, 7H), 6.86-6.73 (m, 3H), 4.68 (m, 2H), 3.84 (m, 1H), 3.53 (m, 1H), 3.31-
3.07 (m, 1H), 2.49 (m, 1H), 2.20 (m, 1H)13C NMR (100MHz, CDCl3) δ 148.42,138.72,129.53,
128.77,127.07,126.70,117.24,112.67,56.71,54.84,32.01,24.79.
Pure epithio monomer and proper proportion levigate KOH powder in an inert atmosphere are added in reaction tube, sets
It in small autoclave, vacuumizes after argon gas displacement, is polymerize in 200 DEG C of constant temperature baths, heating stirring takes out examination after 24 hours
Pipe is added the THF containing appropriate a small amount of diluted acid, so that reactant is dissolved, then which is added drop-wise to the 8 times of volumes that stirred
In methanol, gained precipitation filtering, methanol washs repeatedly, polymerization can be re-dissolved in toluene lay equal stress on be deposited in methanol be able to it is pure
Change, polymerization product is dried in vacuo at 60 DEG C, weighs, and is subsequently used for every test, resulting polymers parameter is shown in Table one.
Embodiment 4：
The present embodiment provides the synthesis of (S) -3- (4,4 '-dimethyl) hexichol amido -1,2- epithio propane polymer；
In 100mL round-bottomed flasks, addition Phenhenzamine (11.0g, 60mmol), (S)-epoxychloropropane (12.01g 130mmol,
e.e.：99.0%), 98% acetic acid of 3mL stirs 48 hours in 60-63 DEG C.Then water (40mL) is added, then with ether (90mL)
Extraction, after diethyl ether solution is dried with anhydrous sodium sulfate, powdered sodium hydroxide (6.0g), mistake after reflux 2 hours is added in filtering
Filter, is removed under reduced pressure ether, and residue obtains yellow oil with pillar layer separation (eluant, eluent: petrol ether/ethyl acetate 10: 1)
(S) -3- (4,4 '-dimethyl) hexichol amido -1,2- propylene oxide.Above-mentioned propylene oxide (10mmol) is taken to be dissolved in 100mL THF
In, thiocyanation amine aqueous solution (60mmol/10mL H are added2O), 36h is stirred at room temperature, water (10mL) is then added, then use second
Ether (20mL × 3) extracts, and after diethyl ether solution is dried with anhydrous sodium sulfate, ether, residue column chromatography point is removed under reduced pressure in filtering
From (eluant, eluent: petrol ether/ethyl acetate 10: 1), yellow oil is obtained, (S) -3- (N- phenyl-N- benzyls) -1,2- epoxies
Propane：Yield 38.7%.(c=1mg/mL, THF, e.e.：98.3%).
Pure epithio monomer and proper proportion levigate KOH powder in an inert atmosphere are added in reaction tube, sets
It in small autoclave, vacuumizes after argon gas displacement, is polymerize in 250 DEG C of constant temperature baths, heating stirring takes out examination after 24 hours
Pipe is added the THF containing appropriate a small amount of diluted acid, so that reactant is dissolved, then which is added drop-wise to the 10 times of volumes that stirred
Methanol in, gained precipitation filtering, methanol washs repeatedly, polymerization can be re-dissolved in THF lay equal stress on be deposited in methanol be able to it is pure
Change, polymerization product is dried in vacuo at 60 DEG C, weighs, and is subsequently used for every test, resulting polymers parameter is shown in Table one.
One bulk polymerization resulting polymers parameter of table
Wherein monomer 1 is 3- (4,4 '-dimethyl) hexichol amido -1,2- epithio propane
Monomer 2 is 3- (N- phenyl-N- benzyls) -1,2- epithio propane.
Comparative example 1
The present embodiment provides (R) -3- (4,4 '-dimethyl) hexichol amido -1,2- epithio propaneMonomerSynthesis, in addition to making
Thiocyanation amine aqueous solution (40mmol/10mL H are substituted with thiocyanation amine powder2O) outside, thiocyanation amine powder is directly dissolved in molten
In agent THF, remaining is same as Example 1.Ultimate yield is：15.6%.
Comparative example 2
The present embodiment provides (S) -3- (4,4 '-dimethyl) hexichol amido -1,2- epithio propaneMonomerSynthesis, in addition to sulphur
A concentration of 10mmol/10mL H of cyaniding amine aqueous solution2Outside O, remaining is same as Example 1.Ultimate yield is：13.8%.
Comparative example 3
It is poly- that the present embodiment provides (S) -3- (4,4 '-dimethyl) hexichol amido -1,2- epithio propaneMonomerSynthesis, in addition to
A concentration of 80mmol/10mL H of thiocyanation amine aqueous solution2Outside O, remaining is same as Example 1.Ultimate yield is：15.2%
It is compared with comparative example by embodiment 1-4, it can be seen that after thiocyanation amine aqueous solution is added, yield
Than the left and right that doubles for being directly added into thiocyanation amine.
It should be appreciated that the purposes of these embodiments is merely to illustrate the present invention and not limits the scope of the invention.
In addition, it should also be understood that, after the technology contents for having read the present invention, those skilled in the art can make the present invention various change
Dynamic, modification and/or modification, all these equivalent forms equally fall within the application protection domain as defined in the appended claims
Within.
Claims (6)
1. a kind of preparation method of epithio monomer, which is characterized in that the structural formula of the epithio monomer be Formula II or formula III,
Wherein R1, R2, R3, R4, R5, R6, R7, R8, R9, R10 be hydrogen atom either alkyl or R1, R2, R3, R4, R5, R6,
It is one or more phenyl ring at adjacent two in R7, R8, R9, R10；
Preparation method includes：
It is reacted in the presence of acetic acid with the epoxychloropropane of optically-active using diaryl-amine and generates open-loop products, then existed in sodium hydroxide
Lower carry out closed loop, obtains the epoxy monomer of optically-active；
The epoxy monomer of optically-active is dissolved into organic solvent, thiocyanation amine aqueous solution is added and carries out the epithio that optically-active is obtained by the reaction
Monomer, a concentration of 40-60mmol/10mL H of the thiocyanation amine aqueous solution2O。
2. the preparation method of epithio monomer according to claim 1, which is characterized in that the organic solvent be cyclic ethers class or
Hydro carbons with loop configuration.
3. the preparation method of epithio monomer according to claim 2, which is characterized in that the hydro carbons is hexamethylene or first
Benzene.
4. a kind of preparation method of the unidextrality spiral polythiaether with skeleton structure, the unidextrality helix poly with skeleton structure
It is R types or S types that thioether, which has poly- [3- diaryl-amine base -1,2- epithios propane] skeleton structure shown in Formulas I, polymer,
In formula：Y1, Y2, Y3, Y4 are phenyl ring or aryl or the phenyl ring containing substituent group or aryl；N is the degree of polymerization=8~10；
It is characterized in that：
The preparation method includes：
The preparation method of 1-3 any one of them epithio monomers is wanted to obtain epithio monomer using such as right；
Epithio monomer is heated to polymerization under initiator initiation, obtains having poly- [3- diaryl-amine bases -1,2- propylene oxide]
The unidextrality spiral polythiaether of skeleton structure.
5. the preparation method of the unidextrality spiral polythiaether according to claim 4 with skeleton structure, which is characterized in that
The initiator is alkali metal hydroxide, metal-alcoholates compound or metallic alkide compound.
6. the preparation method of the unidextrality spiral polythiaether according to claim 5 with skeleton structure, it is characterised in that：
Temperature when heating polymerization is 70-250 DEG C.
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| US11440995B2 (en) | 2018-10-31 | 2022-09-13 | Zhejiang University | Method for preparing aliphatic polythioether |
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| CN108395536B (en) | 2020-10-27 |
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